EP2757176B1 - Revêtement multicouche à haute absorption de l'énergie solaire et faible émissivité thermique, composite cermet associé, leur utilisation et procédés pour leur fabrication - Google Patents

Revêtement multicouche à haute absorption de l'énergie solaire et faible émissivité thermique, composite cermet associé, leur utilisation et procédés pour leur fabrication Download PDF

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EP2757176B1
EP2757176B1 EP14151482.8A EP14151482A EP2757176B1 EP 2757176 B1 EP2757176 B1 EP 2757176B1 EP 14151482 A EP14151482 A EP 14151482A EP 2757176 B1 EP2757176 B1 EP 2757176B1
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layer
tio
niobium
around
composite
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EP2757176A1 (fr
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LAIDANI Nadhira BENSAADA
Ruben BARTALI
Victor MICHELI
Gloria GOTTARDI
Luigi CREMA
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Fondazione Bruno Kessler
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Fondazione Bruno Kessler
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/584—Non-reactive treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/324—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal matrix material layer comprising a mixture of at least two metals or metal phases or a metal-matrix material with hard embedded particles, e.g. WC-Me
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
    • F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/30—Auxiliary coatings, e.g. anti-reflective coatings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
    • F24S70/25—Coatings made of metallic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

Definitions

  • the invention concerns a multilayer coating with high absorption of solar energy and a low thermal emissivity. Moreover, a cermet composite is proposed having high absorption of solar energy and a low thermal emissivity. Processes for producing them are described. The coating and the cermet composite are mainly used in the field of solar thermal systems for producing solar thermal and/or electric energy.
  • Solar thermal systems are devices that make it possible to capture solar light, store it and use it in the most various manners, in particular with the purpose of heating running water, replacing boilers supplied with natural gas or for producing electricity (solar thermal electricity).
  • the photo-thermal conversion efficiency in such systems with average and high temperatures strongly depends upon the optical properties and on the thermal stability of the materials of the components used in the solar collector.
  • Systems are divided into low-temperature systems (up to 120°C), medium-temperature systems (up to around 500°C) and high-temperature systems (around 1000°C) which are used especially in large industrial plants.
  • the solar collector is the core device on which this technology is based.
  • the collectors are crossed by a thermovector fluid canalized in a solar circuit that will conduct it to an accumulator.
  • the accumulator has the function of storing as much thermal energy as possible so as to be able to use it at a later moment, when needed.
  • vacuum tube solar collectors There are various types, the most recent ones are vacuum tube solar collectors.
  • a solar thermal system is always made up of at least the following units: one or more collectors that give up the heat of the sun to the fluid [there are various types of these, from a simple copper plate crossed by a serpentine and painted with black paint (which can be easily damaged and has a high emission in the infrared spectrum), to a selective panel that is treated with titanium dioxide, to the vacuum collector] and a storage tank of the fluid.
  • CSP Concentrating Solar Power
  • Different materials are known having a high absorption of solar energy and a low thermal emissivity that, at low temperatures and at ambient pressure, have the selective capability of greatly absorbing solar light and that have a low thermal emissivity, i.e. with an absorption of at least 0.90 in the visible range and a thermal emissivity of at most 0.10.
  • thermal emissivity of 0.06 at 100°C leads to an emissivity of around 0.10 at 350°C.
  • a low emissivity of 0.06 at 350°C negatively affects the solar absorption since the sun and black body spectra at 350°C slightly overlap and it is necessary for the passage from low reflectance in the field of solar wavelengths to high reflectance in the field of infrared wavelengths to be well defined.
  • the purpose of the present invention is to propose a coating with high absorption of solar energy and a low thermal emissivity and to provide relative materials, in particular cermet composites, with high absorption of solar energy and a low thermal emissivity that can be used in such coatings and at temperatures of around 350°C and in vacuum conditions have a high absorption of solar energy and have a low thermal emissivity.
  • Such coatings are therefore selective, in terms of spectral absorption.
  • Such coatings and materials must be suitable for being used in solar thermal systems.
  • the layer of molybdenum of the coating according to the invention is applied on a substrate of stainless steel, for example on a concentrator tube.
  • TiO 2 is a cermet matrix with a high refractive index, it has a good transparency in the visible range, a high melting point (1843°C) and a good chemical and mechanical stability.
  • Niobium is a refractory reflective metal that has extraordinary heat and wear resistance and has a melting point of 2477°C.
  • the different layers of the coating can obviously contain traces of other elements or composites that are common in the field, and this is due for example to the impurities in the raw materials used.
  • the thin layer of molybdenum acts as an infrared-reflecting layer.
  • the layer of SiO 2 on the other hand acts as an anti-reflective element to visible light.
  • the layers have the order as indicated in claim one.
  • TiO 2 is amorphous.
  • the layer of TiO 2 and niobium is a single layer. This layer has a constant atomic fraction of niobium in the matrix of titanium dioxide, i.e. an atomic fraction that is constant in the entire volume of the layer.
  • the layer of TiO 2 and niobium is a double layer that is made up of two sublayers that are essentially made up of TiO 2 and niobium metal with different concentrations of niobium in TiO 2 , preferably a first base sublayer with a high atomic fraction of niobium and a second sublayer with a low atomic percentage of niobium that has grown on the first sublayer. In this last case the results that can be obtained in terms of absorption of the solar light and of the thermal emissivity are better.
  • the double layer has the advantage of having less reflectance in the UV region (0.3 - 0.4 ⁇ m).
  • said single layer is essentially made up of TiO 2 and niobium metal in which the concentration of niobium in the TiO 2 corresponds to 27 - 34 at.%, preferably to 29.6 - 32.0 at.%, more preferably to 30.2 - 31.4 at.%, even more preferably to around 30.8 at.%.
  • this single layer has a thickness of between 33 and 62 nm, preferably 42.5 - 52.5 nm, more preferably 47.5 nm.
  • said double layer is made up of a first sublayer that is essentially made up of TiO 2 and niobium metal in which the concentration of niobium in the TiO 2 corresponds to 27 - 34 at.%, preferably to 29.6 - 32.0 at.%, more preferably to 30.2 - 31.4 at.%, even more preferably around 30.8 at.% (therefore corresponds to the composition described for the single layer); and by a second sublayer that is essentially made up of TiO 2 and niobium metal in which the concentration of niobium in the TiO 2 corresponds to 12 - 18 at.%, preferably to 14.4 - 15.6 at.%, more preferably to 14.7 - 15.3 at.%, even more preferably around 15.0 at.%.
  • a first sublayer that is essentially made up of TiO 2 and
  • the values for the absorption refer to the entire solar spectrum (0.3 ⁇ m - 4.045 ⁇ m), whereas the emissivity refers to the field 0.3 ⁇ m - 100 ⁇ m wherein the data measured have been extrapolated from 20 ⁇ m to 100 ⁇ m.
  • the first sublayer has a thickness of between 10 and 50 nm, preferably between 26 and 50 nm, more preferably 34 - 42 nm, even more preferably around 38 nm
  • the second sublayer has a thickness of between 17 and 70 nm, preferably of between 17 and 38 nm, more preferably 24 - 31 nm, even more preferably around 27 nm.
  • Another thickness of the second sublayer is 28.5 nm.
  • the layer of molybdenum has a thickness greater than 100 nm.
  • the layer of SiO 2 has a thickness of 50 to 150 nm, preferably 77-93 nm, more preferably around 85 nm.
  • Another aspect of the invention concerns a laminar or tubular material, in particular components of a solar thermal system, which are coated with a coating according to the invention.
  • Tubular materials are preferably vacuum tube solar collectors.
  • a further aspect of the invention concerns a cermet composite with high absorption of solar energy and a low thermal emissivity essentially made up of TiO 2 and niobium metal in which the concentration of niobium in the TiO 2 corresponds to 27 - 34 at.%, preferably to 29.6 - 32.0 at.%, more preferably to 30.2 - 31.4 at.%, even more preferably to around 30.8 at.%.
  • the preferred composite at 350°C has high absorption of 0.93 in the visible range and a lower emissivity in the infrared range (4 ⁇ m) of 0.09.
  • the invention furthermore proposes a cermet composite that is essentially made up of TiO 2 and niobium metal in which the concentration of niobium in the TiO 2 corresponds to 12 - 18 at.%, preferably to 14.4 - 15.6 at.%, more preferably to 14.7 - 15.3 at.%, even more preferably around 15.0 at.%.
  • This second type of cermet is particularly advantageous in combination with the first type of cermet composite according to the above, and precisely in the aspect of the invention that concerns the fact that said first type of cermet composite is in the form of a layer and is coated by a layer of the second type of cermet, as indicated in claim 9.
  • the two types of cermet composites can be comprised in coatings, in particular in coatings that are useful in solar thermal systems. Inside these coatings they can be combined with other antireflective layers in the visible range or infrared reflective layers with respect to those indicated for the coating according to the invention, or they can also be combined with other layers comprising spectral selective absorbing materials.
  • a further aspect of the invention concerns a process for the production of a cermet composite according to the invention in which the niobium is incorporated in the TiO 2 through a co-sputtering vapour deposition method.
  • Another aspect of the invention concerns a process for the production of a coating according to the invention on a substrate that comprises the following steps:
  • the molybdenum can be for example deposited through DC-sputtering of the molybdenum target.
  • the layer of molybdenum is deposited in argon at a pressure of 1-1.5 mTorr. Lower pressures are preferred, but limited by the parameters of the process.
  • on the substrate of molybdenum in the solid state with the composite TiO 2 /Nb is deposited with a controlled thickness and atomic fraction of metal.
  • the cermet layers or film are prepared by incorporating niobium in a matrix TiO 2 by using a physical vapour deposition co-sputtering method.
  • RF radio-frequency
  • niobium is deposited through RF-magnetron-sputtering of a target of niobium.
  • the cermet can also be deposited through sputtering of a target made up of TiO 2 and niobium.
  • the films are prepared by using argon (30 cubic centimetres standard/minute) at 0.01 Torr.
  • the samples are deposited with a floating potential and are not heated from the outside.
  • the silicon dioxide is preferably deposited by means of a reactive sputtering of silicon or through RF-sputtering of a target SiO 2 .
  • RF-sputtering preferred parameters are the use of argon with a pressure of around 3 mTorr.
  • a mixture of argon/oxygen is used (around 3% of oxygen) at a pressure of 5 - 10 mTorr. Both methods obtain films of the same quality.
  • concentrations of niobium and the thicknesses illustrated above for the coating and the cermet composite can be applied mutatis mutandis to the processes according to the invention.
  • a last aspect of the invention concerns the use of cermet composite according to the invention in applications of transformation of the solar light into thermal and/or electric energy.
  • Variant embodiments of the invention are object of the dependent claims.
  • the description of preferred embodiments of the coating, of the cermet composite, of the production processes, of the use according to the invention is given as an example and not for limiting purposes with reference to the attached drawing tables.
  • Fig. 1 illustrates the general scheme of a coating 2 according to the invention that is applied on a stainless steel substrate 4.
  • the coating comprises three layers, and precisely a first layer 6 of molybdenum, a second layer 8 of a cermet composite of a ceramic matrix of TiO 2 which comprises niobium metal and a third layer 10 of SiO 2 .
  • Fig. 2 shows a first embodiment 2a of the coating according to fig. 1 .
  • the coating 2a is applied onto a stainless steel substrate 4.
  • the layers of molybdenum 6 and of silicon oxide 10 are repeated.
  • the layer 8a corresponds to a composite of TiO 2 and niobium metal in which the concentration of niobium corresponds to around 30.8 at.%.
  • Fig. 3 shows a second embodiment 2b of a coating according to fig. 1 .
  • the coating 2b is applied onto a stainless steel substrate 4.
  • the layers of molybdenum 6 and of silicon oxide 10 are repeated.
  • the intermediate layer corresponds to two distinct films, and precisely to a first film 8a' with a composite of TiO 2 and niobium metal in which the concentration of niobium corresponds to around 30.8 at.% and to a second film 8b with a composite of TiO 2 and niobium metal in which the concentration of niobium corresponds to around 15 at.%.
  • the materials of the layers 8a and 8a' are the same, but their thicknesses are different. Example values for the concentrations of niobium inside the composite and for the thicknesses of the different layers are found in the description of the invention.
  • the niobium contained in the composites/coatings according to the invention is found in the metal state.
  • an Auger spectroscopic analysis (AES, Auger Electron Spectroscopy) was carried out by using a PHI 4200.
  • Fig. 4 shows the differential AES spectra of two references, in particular of niobium metal (pure metal film, 99.99%, Goodfellow) and of oxidised niobium.
  • the spectra were acquired after an erosion of the surface layers of the samples for eliminating contaminants and the native oxide formed in contact with the environment.
  • the Auger transitions show substantial differences for the two types of niobium: the differential spectrum for the niobium metal is characterised by a single minimum at 169 eV in the energy range 155-180 eV; whereas for the oxidised niobium, the form of the differential spectrum is different, in that there are two minimums, and for the greater excursion, the energy position is moved towards the low kinetic energies, as it should be for an oxide.
  • the analysis of different transitions of niobium can be used to identify the chemical state of niobium in the composite TiO 2 /Nb.
  • Fig. 5 shows the AES differential spectrum of a TiO 2 /Nb composite according to the invention in which the form of the line for niobium is similar to that of the metal Nb and shows the main characteristic at 169 eV. Niobium is therefore present only in the metal form.
  • Fig. 6 shows together with the solar spectrum and with the emission of a black body normalised to 1 at 350°C the reflectance spectrum in the visible light and in the infrared region of the embodiment of the coating according to fig. 2 , i.e. for a version with TiO 2 /Nb in a single layer (30.8 at.% of niobium).
  • Fig. 7 shows together with the solar spectrum and with the emission of a black body at 350°C the reflectance spectrum in the visible light and in the infrared region of the embodiment of the coating according to fig. 3 , i.e. for a version with TiO 2 /Nb in a double layer (respectively at 30.8 at.% and 15.0 at.% of niobium).
  • the version with a double layer has absorption coefficients which are slightly greater with respect to the version with a single layer.
  • the tool used for measuring the solar spectral field was a UV/VIS/NIR double beam spectrophotometer (Perkin Elmer Lambda 900). It is a dispersive type that uses a white light source and a few grating monochromators to create light with a specific wave length. A detector collects the part of light that is reflected or transmitted according to its setting and transfers it to a computer for further processing. As a reference a Spectralon sample has been used.
  • the tool used for carrying out reflectance measurements in the infrared field was a FT-IR (Fourier Transform Infrared) spectrophotometer TENSOR 27 by Bruker. It is provided with a gold-coated integrating sphere. The measured wavelength goes from 2.5 to 22 ⁇ m (450 cm -1 ). According to standard EN 673, the thermal emissivity should be calculated by covering at least up to 50 ⁇ m. The reflectance is thus extrapolated at 100 ⁇ m.
  • FT-IR Fastier Transform Infrared
  • All the composites/coatings according to the invention are stable at 350°C and in vacuum (5 ⁇ 10 -3 Pa) in terms of mechanical, chemical stability, and of maintaining the optical (thermal absorption/emissivity) properties.
  • the samples had dimensions of 40x40 mm.
  • the heat source was a tube oven (ENTECH, Sweden) with a tube chamber that is situated inside it.
  • the maximum temperature, which was reached at the centre of the oven, was of 1100°C. This means that the temperature was not homogeneous inside the oven.
  • the samples to be treated thermally were always kept at a fixed position inside the oven.
  • a small metal box (100x50x25 mm) was used for containing the samples. The box was placed close to the centre of the oven through a mechanical fixing. Thanks to its thermal mass, the box compensates for the temperature inside the box.
  • a thermocouple mounted on an internal surface of the lid of the box was used for monitoring the temperature and this temperature was considered the temperature of the sample.
  • the chamber was connected to a vacuum system that was provided with an Edwards HT10 diffusion pump with a capacity of 3000 l/s (nitrogen).
  • a gas dosage valve (EVD 010H, Pfeiffer) was installed between the chamber and the pump for controlling the pumping speed so that the pressure in the chamber could be adjusted to the value closest to the actual value in a vacuum system.
  • a compact full range manometer (Balzers PKR 250) was installed on the end of the chamber to monitor the pressure.
  • the selected temperature was 350°C, the pressure 5 ⁇ 10 -3 Pa with an exposure of 240 hours.
  • the invention reached its purpose of proposing a coating and a relative cermet composite which at temperatures of around 350°C and in vacuum conditions (around 5 ⁇ 10 -3 Pa) is characterised in that it has a high solar energy absorption and a low thermal emissivity that are also stable over time.
  • Such cermet coatings/composites are thus, in terms of absorption, spectrally selective.
  • Such coatings and materials are suitable for being used in solar thermal systems.
  • the coating and the materials that are coated in it, the cermet composite, its use and the processes for producing the coating and the cermet composite object of the invention can undergo further modifications or variants that have not been described. Wherever such modifications or such variants are covered by the following claims, they should all be considered protected by the present patent.

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  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)

Claims (12)

  1. Revêtement multicouche à haute absorption d'énergie solaire et à faible émission thermique, appliqué sur un substrat (4), comprenant:
    (a) une première couche de molybdène;
    (b) une seconde couche constituée de TiO2 et de niobium métallique; et
    (c) une troisième couche de SiO2.
  2. Revêtement multicouche selon la revendication 1, caractérisé en ce que ladite seconde couche est une couche unique ou une double couche constituée de deux sous-couches constituées de TiO2 et de métal niobium présentant différentes concentrations de niobium dans le TiO2.
  3. Revêtement multicouche selon la revendication 2, caractérisé en ce que ladite couche unique est constituée de TiO2 et de métal niobium, dans laquelle la concentration de niobium dans le TiO2 est comprise entre 27 et 34 % at., préférablement entre 29,6 et 32,0 % at., plus préférablement entre 30,2 et 31,4 % at., encore plus préférablement est d'environ 30,8 % at.
  4. Revêtement multicouche selon la revendication 2, caractérisé en ce que ladite double couche est constituée d'une première sous-couche constituée de TiO2 et de métal niobium, dans laquelle la concentration de niobium dans le TiO2 est comprise entre 27 et 34 % at., préférablement entre 29,6 et 32,0 % at., plus préférablement entre 30,2 et 31,4 % at., encore plus préférablement est d'environ 30,8 % at.; et d'une seconde sous-couche constituée de TiO2 et métal niobium, dans laquelle la concentration de niobium dans le TiO2 est comprise entre 12 et 18 % at., préférablement entre 14,4 et 15,6 % at., plus préférablement entre 14,7 et 15,3 % at., encore plus préférablement est d'environ 15,0 % at.
  5. Revêtement selon la revendication 3, caractérisé en ce que ladite couche unique présente une épaisseur comprise entre 33 et 62 nm, préférablement entre 42,5 et 52,5 nm, plus préférablement est d'environ 47,5 nm, en ce que la couche de molybdène présente une épaisseur supérieure à 100 nm et en ce que la couche de SiO2 présente une épaisseur comprise entre 50 et 150 nm, préférablement entre 77 et 93 nm, plus préférablement est d'environ 85 nm.
  6. Revêtement selon la revendication 4, caractérisé en ce que ladite première sous-couche présente une épaisseur comprise entre 10 et 50 nm, préférablement entre 26 et 50 nm, plus préférablement entre 34 et 42 nm, encore plus préférablement de 38 nm, en ce que ladite seconde sous-couche présente une épaisseur comprise entre 17 et 70 nm, préférablement entre 17 et 38 nm, plus préférablement entre 24 et 31 nm, encore plus préférablement de 27 nm, en ce que la couche de molybdène présente une épaisseur supérieure à 100 nm et en ce que la couche de SiO2 présente une épaisseur comprise entre 50 et 150 nm, préférablement entre 77 et 93 nm, plus préférablement est d'environ 85 nm.
  7. Matériau laminaire ou tubulaire, en particulier des composants d'un système solaire thermique, revêtus d'un revêtement selon l'une quelconque des revendications 1 à 6.
  8. Composite en cermet, constitué d'un revêtement, à haute absorption d'énergie solaire et à faible émissivité thermique, constitué de TiO2 et de métal niobium, dans lequel la concentration de niobium dans le TiO2 est comprise entre 27 et 34 % at., préférablement entre 29,6 et 32,0 % at., plus préférablement entre 30,2 et 31,4 % at., encore plus préférablement elle est d'environ 30,8 % at.
  9. Composite en cermet selon la revendication 8, caractérisé en ce que ledit composite en cermet se présente sous la forme d'une couche recouverte d'une couche d'un composite en cermet constitué de TiO2 et de métal niobium, dans lequel la concentration de niobium dans le TiO2 est comprise entre 12 et 18 % at., préférablement entre 14,4 et 15,6 % at., plus préférablement entre 14,7 et 15,3 % at., encore plus préférablement elle est d'environ 15,0 % at.
  10. Procédé de production d'un composite en cermet selon la revendication 8 ou 9, dans lequel le niobium est incorporé dans le TiO2 via un procédé de dépôt en phase de vapeur par co-pulvérisation cathodique de plasma radiofréquence dans une atmosphère inerte.
  11. Procédé de fabrication d'un revêtement selon l'une quelconque des revendications 1 à 6 sur un substrat comprenant les étapes suivantes:
    (a) la préparation d'un substrat, préférablement en acier inoxydable;
    (b) le dépôt d'une couche de molybdène sur ledit substrat;
    (c) le dépôt sur ladite couche de molybdène d'une couche d'un composite constitué de TiO2 et de métal niobium via dépôt en phase de vapeur par co-pulvérisation cathodique de plasma radiofréquence dans une atmosphère inerte;
    (d) le dépôt d'une couche de SiO2 sur ladite couche dudit composite de TiO2 et du niobium.
  12. Utilisation dudit composite en cermet selon l'une quelconque des revendications 8 ou 9 dans des applications de transformation de la lumière solaire en énergie thermique et/ou électrique.
EP14151482.8A 2013-01-16 2014-01-16 Revêtement multicouche à haute absorption de l'énergie solaire et faible émissivité thermique, composite cermet associé, leur utilisation et procédés pour leur fabrication Not-in-force EP2757176B1 (fr)

Applications Claiming Priority (1)

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IT000006A ITVI20130006A1 (it) 2013-01-16 2013-01-16 Rivestimento multistrato a elevato assorbimento di energia solare e a bassa emissività termica, un relativo composito cermet, un suo uso e procedimenti per la loro produzione

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EP2757176B1 true EP2757176B1 (fr) 2018-10-03

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WO2016069174A1 (fr) * 2014-10-29 2016-05-06 University Of Houston System Stabilité thermique améliorée d'absorbeurs solaires à sélectivité spectrale à base de cermet constitué de plusieurs métaux
ES2575746B1 (es) * 2014-12-31 2017-04-19 Abengoa Research, S.L. Estructura selectiva solar con autolimpieza resistente a altas temperaturas
EP3527911A1 (fr) 2018-02-16 2019-08-21 Cockerill Maintenance & Ingenierie S.A. Revêtement absorbeur appliqué par pulvérisation thermique de haute performance
CN115142015B (zh) * 2021-12-14 2024-04-30 常州瞻驰光电科技股份有限公司 一种高吸收光学镀膜材料及其制备方法

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IN185567B (fr) * 1991-07-19 2001-03-03 Univ Sydney
ITRM20080113A1 (it) * 2008-02-29 2009-09-01 Enea Ente Per Le Nuove Tecnologie, L Energia... Metodo per la fabbricazione di un rivestimento spettralmente selettivo a base cermet per il tubo ricevitore di un concentratore solare e materiale cosi ottenuto
US20100092747A1 (en) * 2008-10-14 2010-04-15 Northwestern University Infrared-reflecting films and method for making the same
DE102009022059A1 (de) * 2009-05-20 2010-11-25 Schott Solar Ag Strahlungsselektive Absorberbeschichtung und Absorberrohr mit strahlungsselektiver Absorberbeschichtung
DE102009049471B3 (de) * 2009-10-15 2011-04-07 Schott Solar Ag Strahlungsselektive Absorberbeschichtung und Absorberrohr mit strahlungsselektiver Absorberbeschichtung
PT2606290T (pt) * 2010-11-19 2017-12-14 Siemens Concentrated Solar Power Ltd Revestimento absorvente de energia solar, disposição do revestimento num substrato, método para fabrico da disposição e utilização da disposição

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ITVI20130006A1 (it) 2014-07-17
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